BRPI0709195A2 - disseminated or dry spaced granule, method of production thereof and method of supplying an active chemical agent to a site to be treated - Google Patents

Abstract

DISSEMINATED GRANULATE OR DRY SPREAD, METHOD OF PRODUCTION OF THE SAME AND METHOD OF SUPPLYING A CHEMICAL AGENT ACTIVE TO A SITE TO BE TREATED. A dry disseminated or spreadable granule having an applied composition comprising an active chemical agent capable of forming a microemulsion upon dilution with water.

Description

DETAILED DESCRIPTION REPORT FOR "DRY SEED OR SPREAD BEAN, SAME PRODUCTION METHOD AND PROCEDURE FOR PROVIDING A CHEMICAL AGENT FOR A SITE TO BE TREATED".

This invention relates to dry dispersible or dispersible granule compositions; and their use as carriers of active chemical agents such as herbicides, insecticides and other pesticides; and methods for the preparation and use of said compositions. More specifically, the technology relates to a formulation for use in the form of dry granules and methods of preparing it, and even more specifically to its use in the widespread or spreadable supply of chemical agents. soil and / or vegetation active.

Background of the Invention

A pesticide is a bioactive material that destroys or inhibits the action of plant or animal pests. The general term pesticide includes insecticides, herbicides, fungicides, plant growth regulators, emitted rodenticides.

Pesticides are widely used in the soil and are applied to the leaf to desired plants, such as ornamentals, food and fiber and peat plants, to control weeds, insects and disease. Typically, pesticides are formulated in conventional forms such as dusts, granules, wettable powders and emulsions using techniques well known in the art. A preferred means of pesticide application for both consumers and professional applicators is dry granules for use in the widespread supply of pesticides.

Granular pesticides are important commercial products because of their ability to eliminate vegetation, disease, unwanted insects and the like and their ease of application, either by manual or mechanical means. The granular pesticide may be a pesticide applied to a feed material such as clay or ground corn cob, or it may be a fertilizer / pesticide combination, wherein the pesticide is applied to a fertilizer material. In a granular form, a pesticide is impregnated with or is absorbed on an inert material or a fertilizer material. The granular depesticide product is applied to soil and / or vegetation by direct spreading of pesticide granules onto the soil and / or vegetation at an appropriate dosage rate.

The dry granules of the present invention are those granules that can be applied with a dry spreader or manually to a target area and when exposed to water via, for example, rain or irrigation, which allow pesticidal material to migrate back from the vehicle later.

The granules of the present invention include inert carriers that do not readily disintegrate in irrigation. In order to facilitate dopesticide spreading, granules of the present invention may also be prepared to readily disintegrate when exposed to water and to spread the area affected by the pesticide. Such granules are often prepared from wood dust, diatomaceous earth compositions or mineral components such as limestone or dolomite, and may contain surfactants and / or binders to aid in the disintegration and dispersion of the granules when exposed to water. Pesticide supply granules also include fertilizers impregnated with a pesticide.

Microemulsions, another conventional formulation for active chemical agents, are a subclass of emulsions and are a thermodynamically stable dispersion of a liquid phase into another, are stabilized by an interfacial or surfactant film. Microemulsions are typically clear solutions and contain emulsion droplets having an average particle size of about 0.01 to 0.1 microns. Such formulations typically contain an oil phase comprising at least a pesticidally active ingredient and emulsifiers. Substantially water-insoluble pesticides that are liquid at room temperature may be dispersed when they are in water. When the active ingredients are solid or high viscous, water-immiscible organic solvents may be used to dissolve them. Typically, the amount of emulsifiers needed in a microemulsion is higher than that in an emulsion. Microemulsifiable concentrates contain high levels of active ingredients and emulsifier and upon dilution in water form compositions containing emulsion droplets having an average particle size of about 0.01 to 0.1 microns. One or more emulsifiers may be used in the preparation of microemulsifiable concentrates of the present invention. The concentrates may comprise a single surfactant, for example a nonionic surfactant such as a castor oil condensate product and a polyC 2-4 alkylene oxide. Combinations of strongly hydrophobic nonionic surfactants (preferably those having a hydrophilic lipophilic balance (HLB)> 13) and hydrophobic anionic surfactants are also preferred emulsifiers for microemulsions and microemulsifiable concentrates.

Microemulsions and microemulsifiable concentrates are well known in the art as shown by, for example, European Patent Application No. EP 160 182 A2; U.S. Patent Nos. 4,870,103; 4,904,695; 4,954,338; 4,973,352; 5,242,907; 5,317,042; 5,326,789; 5,334,585; U.S. Patent Application Publications Nos. 2003/087764, 2004/0132621 and 2005/0043182; PCT Publication WO 99/65300 and WO 02/45507.

Granular pesticides of the present invention comprise a pesticide or mixture of pesticides combined in, absorbed, impregnated or coated on a solid substrate. The solid substrate may be inert material, for example clay, and / or a fertilizer material, for example urea / formaldehyde, potassium chloride, ammonium compounds, phosphorus compounds, sulfur, plant nutrients and micronutrients. similar, mixtures and combinations thereof, both naturally occurring and synthetic organic or inorganic materials.

An important fraction of a disseminated granule formulation includes the release and coverage of the active chemical agent (s) to the surrounding soil soil after application of the granule. Two mechanisms for the release of the active chemical agent (s) contained in or on the granule vein are: (1) abrasion of pesticide-active material from the vein, or alternatively (2) granular carrier disintegrants raise the pesticide-active material in the vicinity of the granule origin. In the above-mentioned mechanisms, the pesticide-active material is moved from the granule site by the dynamic force of water passage from the granule site. A disadvantage to these mechanisms is that pesticide-active materials that are substantially insoluble in water are not associated with water passage.

A common problem associated with known granules is the inability of the active chemical agent (s) to leave the granule. The inability to leave the vehicle is common when the active chemical agent (s) absorbs too deeply and deeply into the inert vehicle, or the agent (s). The active chemical (s) are too tightly and firmly adhered to the inert carrier.

Known methods of increasing the coverage of a pesticidally active material to the surrounding area of the granule include the use of a dispersible granule that breaks on exposure to water to cover a larger surface area, thereby enhancing agent distribution (). chemical (s) active over a specified area. While these granules improve the area of active chemical coverage, they do not increase the ability of the active chemical to migrate further from the granular vehicle's external dolimite. Examples of dispersible granules are provided in U.S. Pat. 6,231,660; 6,375,969; 6,416,775 and 6,613,138.

It would be advantageous to create a granular formulation containing a pesticidally active material that would readily be associated with water migration, thereby increasing the coverage of the pesticidally active material in the soil. The present invention combines the known formulation methods of dry dispersed microemulsions and seeding granules to accomplish this objective.

Summary of the Invention

The present invention relates to a granular formulation with increased biological activity. Granular compositions of the present invention are obtained by coating, absorbing or impregnating a carrier material of a microemulsifiable concentrate formulation containing at least one active chemical, wherein the formulation is capable of deforming a microemulsion when diluted. in water. The granular formulation is a dry composition that can be applied to soil and / or vegetation by spreading or spreading application. Upon application and subsequent irrigation or aquaerea the active chemical agent associates with water and readily allows the active chemical agent to spread to the surrounding site. This association allows the active chemical agent to be transported through water, thereby increasing the coverage of the chemical agent.

Detailed Description of Preferred Embodiments

The present invention relates to a granular formulation with increased biological activity. The granular compositions of the present invention are obtained by coating, absorbing, or impregnating the carrier material with a microemulsifiable concentrate comprising at least one water-insoluble active chemical. Subsequent technology refers to a method for producing and using the granular formulation.

In this report, the term "active chemical agent" is intended to cover pesticide-active materials as well as materials that are applied to a plant or its location to achieve a beneficial effect. Agents include, for example, herbicides, bactericides, fungicides, insecticides, miticides, acaricides, molusticides, nematicides, plant growth regulators and insect growth regulators. In the case of plants, the pests will be weeds or other undesirable vegetation in a particular location. Lower organisms are also included within the scope of the invention, particularly where they are harmful in a particular location, such as fungi, algae and other microorganisms. The term active pesticide materials and pesticides will include substances that control such persons, that is, plague-destroying substances and / or substances that stop multiplying or reproducing.

The microemulsifiable concentrated formulations of the present invention which are capable of forming a microemulsion when diluted in water comprise emulsifiers and active chemical agents. The formulations are applied to a granule carrier for use as a dry dispersed granule. As used herein, the term "microemulsifiable concentrate" includes concentrates of the active chemical agents which upon dilution in water form optically transparent formulations having an emulsion droplet size of between 0.01 and 0.1 microns, although the emulsion - they are formed at dilution not thermodynamically stable. For the purpose of this invention, the term "optically transparent" is defined as compositions having no or almost no transmitted light attenuation, preferably a complete lack of any non-uniformity when viewed in bulk, in bottles or tubes. test, by strong transmitted light.

This includes microemulsions that may appear slightly misty due to the presence of emulsion droplets having an emulsion droplet size in the upper size range of the described ranges.

The terms "water-insoluble" and "substantially water-insoluble" as used herein mean that for all practical purposes, the solubility of the compound in water is sufficient to produce the practically usable compost in an end-use formulation without any modification or to increase its solubility or dispersibility in water.

Substantially water-insoluble active chemical agents, such as pesticides, which are liquid at room temperature can be dispersed with water alone emulsifiers in need of a solvent. Inasmuch as the substantially water-insoluble pesticide active ingredient is a high viscosity liquid or a solid, solvents may be used to dissolve the substantially water-insoluble pesticide active ingredient to form a low viscosity liquid. Suitable solvents may be determined by that in the art and include water immiscible and water miscible solvents.

Water-immiscible solvents in which the active chemicals may be dissolved include aliphatic and aromatic hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene, mineral or que-rosene, substituted or naphthalene mixtures, commercially monolepylated aromatic mixtures available under the trademarks SOL-VESSO®, ISOPAR®, SHELLSOL®, PETROL SPEZIAL® and AROMATIC®, halogenated hydrocarbons such as methylene chloride, chloroform and o-dichlorobenzene; phthalates, such as dibutyl phthalate or dioctyl phthalate; ethers and esters, such as ethylene glycol monomethyl or monoethyl ether, fatty acid esters; Iactones such as butyrolactone; ketones such as cyclohexone; higher alcohols such as hexanol and octanol; plant oils such as castor oil, soybean oil, cottonseed oil and their possible methyl esters; as well as soybean oil or epoxidized coconut oil. Preferred water-immiscible solvents are aliphatic and aromatic hydrocarbons, petroleum based esters, fatty acid esters (e.g. WITCONOL 2309), dipropylene glycol monomethylether (e.g. DO-WANOL DPM) and castor oil.

Suitable alkyl alkanoate ester solvents include C6 -C13 alkyl C1-4 alkanoates such as the oxohexyl, oxoheptyl, oxo-octyl, oxo-nonyl, oxo-decyl, oxo-hexane, propanoate and butanoate formats. dodecyl and oxo-tridecyl; preferably C6 -C13 alkyl acetates. Such materials are generally commercially available or may be produced by those of ordinary skill in the art. Alkyl numbers of the above alkyl acetate are commercially available. Particularly advantageous C6 -C13 alkyl acetate are available from Exxon Mobil Corporation under the general trademark ".

Suitable polyhydric alcohol condensates of polyhydric alcohol include propylene glycol; dipropylene glycol; polyC 2-6 alkylene glycols and preferably poly (C 2-6 alkylene) glycol derivatives and derivatives such as polypropylene glycol [M.W. 2000-4000], polyoxyethylene polyoxypropylene glycols, polyoxypropylene polyoxyethylene glycols, diethylene glycol, polyethylene glycol [M.W. 200-4000 amu], methoxy polyethylene glycols 350, 550, 750, 2000, 5000; glycerol, ethoxylated glycerol; propoxylated glycerol; sugar alcohols and their alkoxylated derivatives such as xylitol, mannitol, sorbitol, ethoxylated sorbitol, hydroxypropyl sorbitol; hexylene glycol (2-methyl-2,4-pentanediol); 1,3-butylene glycol; 1,2,6-hexanetriol; ethoxadiol USP (2-ethyl-1,3-hexanediol); Vicinal C 15 -C 18 glycol and trimethylolpropane polyoxypropylene derivatives and short chain up to 7 carbons, preferably up to 4 carbons of aliphatic glycols, and glycerin.

Particularly suitable water-immiscible solvents include fatty acid methyl esters derived from fats and oils such as methyl oleate, n-octanol, alkyl phosphates such as tri-n-butyl phosphate, propylene carbonate and isoparaffin solvents.

Water miscible solvents such as tetrahydrofurfuryl alcohol, gamma butyrolactone, N-methyl-2-pyrrolidone, tetramethylurea, dimethylsulfoxide, Δ, Ν-dimethylacetamide and dimethylformamide may be used as co-solvents with the water immiscible solvents described above. .

Selection of suitable surfactant (s) for the e-mulsifier system can be produced by the skilled in the art without improper experimentation. Typically, the amount of surfactants required to form a microemulsion is greater than that for an emulsification. The emulsifier system comprises at least one surfactant capable of forming a microemulsion of the water-diluting active chemical, for example, at least one nonionic surfactant such as condensation product and a P10 Cl2-4 alkylene oxide. Combinations of strongly hydrophobic nonionic surfactants (HLB> 9, preferably> 13) and hydrophobic anionic surfactants are also preferred emulsifiers for the formation of microemulsions.

The term "surfactant" as used in this report means a chemical that acts as a surface active agent that can provide foaming, wetting, dispersing and emulsifying properties and which is cationic, anionic, nonionic or amphoteric.

As co-surfactants, low HLB nonionic surfactants or (C4 to C10) lower alkyl alcohols may be used to lower the HLB of the formulation and to reduce surface tension between water and oil. Solvents such as methyl esters of fatty acid having a carbon chain length of 8 to 12 may provide the desired emulsification and solubility characteristics. Choosing an appropriate surfactant and co-surfactant, if necessary, and the other components of the microemulsifiable concentrate possible; normal skill in technique without self-experimentation. A useful guide for the preparation of emulsifications can be found in U.S. patent no. 5,242,907, the contents of which are incorporated herein by reference. The amount of surfactants required to emulsify an oil will depend on the amount of oil in the emulsion, more specifically at the interfacial surface that is proportional to the amount of emulsified oil at a constant particle size.

The emulsifier system may comprise a single surfactant, but in preferred embodiments it is more advantageously a combination of surfactants comprising at least one anionic or cationic surfactant and at least one nonionic surfactant. Preferably, the emulsifier system comprises surfactant (s) in an amount of from about 5% to about 40% by weight of the emulsifiable concentrate. Useful detestative examples include nonionic surfactants selected from the group consisting of (1) a mono- C2-6 alkyl ether of a POCl2-4 alkylene oxide block copolymer having at least a first polyalkylene oxide block region and a second block polyalkylene oxide region wherein the polyalkylene oxide in said first region is different than polyalkylene oxide in said second region. Preferably, the C 2-6 alkyl ether moiety is a C 3-5 alkyl ether, more preferably a C 4 alkyl ether, of the alkylene oxide block copolymer. Also preferably, the alkylene oxide block copolymer moiety is preferably an ethylene / propylene oxide block copolymer.

Preferably the ethylene oxide moiety is from about 10 to about 90 mole% to about 25 to about 75 mole% of the block compound. A particularly preferred material is available under Etilan NS-500LQ trademark, available from Akzo Nobel; (2) a castor oil condensation product of a polyC 2-4 alkylene oxide. Preferably the alkylene oxide moiety is ethylene oxide. Preferably the alkoxylation degree is from about 10 moles to about 100 moles of alkylene oxide per mol of castor oil, more preferably about 20 moles to about 70 moles of alkylene oxide per mol of castor oil. . A highly preferred alkoxylated castor oil is available under the trademark Agnique CSO-36, available from Cognis .; (3) a mono- or diester of a C12-24 fatty acid and P0NC2-4 alkylene oxide, where the fatty acid groups may be the same or different. Preferably, the fatty acid groups are the same when two such groups are present. Also preferably, the fatty acid groups are C12-20 fatty acid groups, more preferably C12-18 fatty acid groups, more preferably lauroyl, oleic, caprylic or myristolic acid. In addition, the oxide portion of POCl2-4 alkylene is preferably polyethyloxy and the number of alkylene oxide groups in the oxide portion of PO POC2-4 alkylene is preferably from about 2 to about 40 repeating units. Highly preferred materials of this type include Kessco PEG 400DL (Stepan) and Emerest 2620 (Cognis).

In a particular embodiment, the formulation of the present invention comprises, as a nonionic surfactant, propylene oxide (PO) and ethylene oxide (EO) copolymer and / or an ethoxylated phenol trystyrene. A suitable PO and EO copolymer It is an alpha-butyl-omega-hydroxypoly (oxypropylene) with poly (oxyethylene) block polymer and has a molecular weight of 2400 to 3500. Commercially available examples of such copolymer are Toximul®, Witconol® and Atlas®. In a particular embodiment of the present invention, the copolymer is present in an emulsifiable concentrate at from about 0.5 to about 10 wt% and preferably about 1 to 5 wt%. A suitable phenol ethoxylated trystyrene is alpha- [2,4,6-tris [1- (phenyl) ethyl] phenyl] omega hydroxy poly (oxyethylene). Suitably, the poly (oxyethylene) content yields on average from about 4 to about 150 moles. A commercially suitable example of such surfactant is Soprofor BSU®. In one particular embodiment, such surfactant is present in the concentration at about about 1 and about 15 wt% and preferably from 6 to 10 wt%.

Suitable anionic surfactants include a poly (1,2-ethanediyl) alpha-C 1-10 alkyl-omega hydroxy phosphate or sulfate and / or a C 1-13 alkylbenzenesulfonic acid. Preferably, a poly (oxy-1,2-ethanediyl) alpha-C10-15 alkyl omega hydroxy phosphate or sulfate is a poly (oxy-1,2-ethanediyl) alpha tridecyl omega hydroxy phosphate or sulfate. Also, the (oxy-1,2-ethanediyl) portion of the compound is present at about 3 to about 9, preferably about 6 repeating units per molecule. A suitable compound for poly (oxy-1,2-ethanediyl) alpha-C10-15 alkyl omega hydroxy phosphate is available as Stepfac 8181 (Stepan). A suitable compound for C10-13 alkylbenzenesulfonic acid is Biosoft S-100 (Stepan). Additional suitable anionic surfactants include ethoxylated phosphate and sulfate derivatives of ethoxylated phenols such as - [EO] 2-2o-di and triestyrylphenols, nonylphenols, dinonylphenol and octylphenols.

Where salts of the phosphate or sulfate group are desirable, the salt may be a salt of any base as long as the base is not incompatible with any of the other ingredients including the active chemical agent (s). Particularly suitable are alkali metal, alkaline earth metal phosphate salts, ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a lower mono-, di- or trialkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl propylamine, or a mono-, di- trihydroxy-lower alkylamine, for example mono-, di- or triethanolamine.

In another embodiment, the anionic surfactant is a styryl phenol polyethoxy ester phosphate. A suitable anionic surfactant is alpha- [2,4,6-tris [1- (phenyl) ethyl] phenyl] omega-hydroxy poly (oxyethylene) phosphate. In particular, this compound is present as a mixture of phosphate esters of monohydrogen and dihydrogen and the corresponding ammonium, calcium, magnesium, potassium, sodium and zinc salts. Suitably, the content of poly (oxyethylene) produces on average from about 4 to about 150 moles. A commercially available example of this surfactant is Soprofor 3D33®. In a particular embodiment, such surfactant is present at between about 5 and about 10% by weight.

Suitable cationic surfactants for use in the present invention include C14-20 alkoxylated PolyC2-4 fatty amines, preferably C12-18 alkoxylated polyC2-4 fatty amines, more preferably an alkoxylated P0C1-4 tallow. The alkoxylated polyC4-4 moiety of such a component is preferably present in either 2-8 (more preferably 2-5) repeating units per molecule or the desecomponent alkoxylated polyC4-4 moiety is preferably present in about from 14 to about 18 (more preferably about 16) repeating units per molecule or more is preferably [EO] 2-2- and mixtures thereof. Particularly useful amine compounds include Toximuls such as TA-2, -3, -4, -5, -6, -7, -7, -8, -9, -10, -11, -12, - 13, -14, -15, -16, -17, -18, -19, and -20 (Stepan); and their mixtures. Additional suitable cationic surfactants include fatty acid amino alkanol such as, for example, Witcamides (Witco).

Preferred water-insoluble active chemicals include those pesticides that are substantially water-insoluble active chemical, sometimes referred to herein briefly as a "water-insoluble" active ingredient even though it has measurable water solubility. Such active ingredient preferably has a water solubility at 20 ° C, not more than about 5000 mg / l. Especially preferred water-insoluble active ingredients useful in the present invention have a deionized water solubility at 20 ° C, no more than about 2000 mg / l.

Pesticides and pesticide-active materials include, without limitation, herbicides, fungicides, insecticides, miticides, acaricides, molus-cicidase, nematicides, bacteriocides, plant growth regulators, and insect growth regulators. Substantially water-soluble active ingredients suitable for use in the present invention include, but are not limited to, the indicated pesticides as well as mixtures thereof. The common name used to designate individual compounds can be found from various sources including The Pesticide Manual, 12th edition, 2000, British Crop Protection Council.

Fungicides useful in the present invention include azoxystrobin, bi-tertanol, chlorothalonyl, cyproconazole, cyprinazole, diphenoconazole, fenpiclonyl, fenpropidin, fenpropimorph, fludioxonil, furalaxyl, mefenoxam (r-metallaxyl), metallaxyl, miclobutanil, pyrazixane, oxadixyl, -roquilon, thiabendazole, thiophanate-methyl, triadimephon, triadimenol and trifloxystrobin;

Insecticides useful in the present invention include abamectin, bi-phenthrin, bromopropylate, carbaryl, chlorpyrifos, clothianidine, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, beta-cypermethrin, cyromazine, difentiuron, emamectin benzoate, phenoxycarbate, furoxycarbate, taoxycarbalin, furoxycarbate, , lufenuron, metidation, organophosphorus compounds, permethrin, profenophos, pimetrozine, tefluthrin, tiacloprid and thiametoxam;

Herbicides useful in the present invention include acetochlor, amethrin, butafenacil, chlortoluron, clodinafop, dimetachlor, dimethenamid, dimethanamid-P, phenlorim, fluazifop-p-butyl, flumeturon, flumetsu-lamol, mesotrione, S-metolachlor, norflurazon, pretylachlor, prodiamiin, promethrin and pyridate;

Growth regulators such as cimectacarb, flumetrali, paclobutrazol and trinexapac-ethyl;

Protectors such as fluxophenime, benoxacor, cloquintocet shake it, diclormid, flurazole; and

Plant activators such as acibenzolar-s-methyl.

Granular materials suitable for use in preparing granular formulations of the present invention include those described in U.S. Pat. 4,015,973; 4,954,134; 5,019,564; 5,078,779; 5,207,389; 5,228,895; 5,242,690; 5,739,081; 6,180,565; 6,231,660; 6,375,969; 6,416,775; 6,579,831; 6,613,138. and U.S. Patent Application Publication Nos. 2005/0113257, the contents of which are incorporated herein by reference.

Granular formulations offer significant advantages in packaging, ease of handling and safety over liquid formulations. While not limited to any particular size, the granules of the present invention typically have an average particle size in the range of from about 0.1 to about 10 mm, preferably from about 0.25 to about 5 mm, and more preferably from about 0.5 to about 3 mm, although external sizes of this range may be used.

The granules may be virtually any shape desired, for example spheres, cylinders, ellipses, bars, cones, discs, needles and irregular shapes. Ideally, the granules are approximately spherical and have a soft surface, which gives the desired flow characteristics mass-shaped granules.

Small granules, for example granules about 0.1 to about 3 mm in diameter, preferably of uniform size, tend to be free flowing and low dusting. Although granular compositions may have high bulk densities, for example greater than 0.0016 kg / dm3 (60 pounds per cubic foot), it is sometimes advantageous to use smaller granules with a lower bulk density to effectively transport and distribute the required amount. pesticide active material without excessive amounts of inert vehicle.

Preferably the granules retain their physical integrity during handling and spreading, and in the case of dispersible granules typically disintegrate when irrigation or downpour water is applied to the particle. In moistening, these granules can be disintegrate (flowering) to cover the soil surface. This flowering can cover an area often the original area covered by the bead.

Microemulsifiable concentrates may be applied to the granules such that the active chemical agents may be charged to an amount up to about 30 weight percent of the granules. Active chemicals can be homogeneously distributed throughout the granule, spray-impregnated, or coated onto the granules.

In addition to the emulsifiable concentrate components, in general, granules may include fillers (also called a carrier), surfactants (which term may include dispersants and wetting agents) and auxiliary agents such as binders, stabilizers and buffering agents. The filler material may be inert, or may serve a biological function, such as acting as a fertilizer. The filler material as well as the other components preferably would not degrade the pesticidally active material during granule preparation or long term storage or use in the field. Those of skill in the art may readily select appropriate bead components to meet these criteria.

Typically, the filler particles are finely divided filler particles, and may include inert ore fillers. The particle size of the filler material will depend on the final use of the granule.

The absorbance of the granules is believed to result in part inclusions of voids between the finely divided particles. Correspondingly, the degree of sealing will influence the degree of absorbance of the granules. Absorbance can also be varied by choosing different filler materials that affect the seal. The degree of absorbance can be finely tuned later by use of a mixture of different filler materials. For example, hot processed expanded perlite fillers tend to lead to highly absorbent granules, while talc or mica fillers lead to less absorbent granules. The degree of absorbance of a granule can thus be varied by varying the ratio of hot processed perlite to mica.

Fillers may be inert compounds which, in application, break for a time, but provide no other property, or they may themselves provide a useful function in addition to breaking apart for a time to release pesticide-active material.

In one aspect, the filler materials are water insoluble. The finely divided filler material itself may be absorbent, as in the case of diatomaceous earth, attapulgite or zeolites, but this is not essential as it is the total absorbance of the granule rather than the individual particles that is important for the work of the invention. However, the total absorbance of granules usually increases when absorbent particles are used.

Inert vehicles or fillers include mineral components such as dolomite and limestone, light weight additives such as expanded comosilica, fine ash, hydrated lime, wheat flour, ore flour, ground wheat straw, pulp and flour. soy Mineral and clay soil such as bentonite, kaolin, attapulgite, diatomaceous earth, zeolites, calcium carbonate, talc, muscovite mica and fabricated materials such as precipitated silicas and aluminum silicate, molten potassium sodium (hot-processed perlite or coal) Preferred materials include hot-processed perlite, talc and muscovite mica, and combinations of such materials.The generally plaque-like particle shape of these materials allows them to separate more readily when granules. (manufactured by extrusion, drum granulation or other media) are dispersed in water Additional filler materials include finely ground wood particle agglomerate comprising about 10% by weight of a urea-formaldehyde resin, and wheat straw flour resulting from the finely ground wheat straw particle which includes a diphenylmethane diisocyanate resin. In either case, the additional resin may aid in the production of a granular substrate that does not degrade during handling but disrupts exposure to water. Other inert compounds that satisfy bulk density and size specifications may also be used.

In one aspect of the invention, the filler material functions as a fertilizer. Fertilizers typically provide at least one of the plant nutrients of nitrogen, phosphate or potassium. Representative vehicles that function as fertilizer components include urea, sulfur-coated urea, isobutylidene diurea, ammonium nitrate, ammonium sulfate, ammonium phosphate, triple superphosphate, phosphoric acid, potassium nitrate, potassium metaphosphate , potassium chloride, dipotassium carbonate, potassium oxide and a combination thereof. Soil nutrients include calcium, magnesium, sulfur, iron, manganese, copper, zinc, their oxides, their salts and their combinations. Modification materials include natural organic products such as humic acid, coarse blood meal, coarse bone meal, coarse seed meal, poultry meal and coarse soy flour; coarse meat flour; animal residue from various animal sources; activated sludge, hydrolyzed animal hair, fish by-products; chitin; compounds; and their combinations.

A binder may be used to agglomerate the components of the granules. When present, the binder may typically be used in an amount up to about 20 weight percent (dry basis) of the granular composition, more typically between about 2 to about 20 weight percent. The binder binds the ingredients to a granular substrate that resists friction and will not rapidly degrade, and thus substantially maintains particle size during handling. Examples of suitable binders include beer yeast condensed solubles, lignosulphonate, sodium carbonate lignin, sugarcane syrup, beet syrup, beet syrup, sugar free beet syrup, whey, starch, soybean soluble solvents. of sugarcane or the like, hydrolyzed collagen, amino acid solutions, cellulose derivatives, or cellulose-based polymer binders. Other water soluble binders having equivalent properties for, for example, canned condensate soluble solids may also be used.

The binder may be added to the composition as a solution. The solution is typically provided as a water-based paste having about 40 to about 50 weight percent solids and weighing about 1,190 kg / l (10 pounds per gallon). The binder may also be added and mixed with other dry ingredients, subsequently mixing an amount of water.

Additional auxiliary agents such as surfactants, dispersants, disintegrating agents, wetting agents and the like may be added where desired to modify the properties of the granules.

U.S. Patent 1,304.54 describes four basic methods for preparing granular formulations. The four methods are extrusion: applying a surface coating on a granule; absorption of an active substance into a granule; and applying a binder and active material to a suitable powder and forming granules from the powder mixture.

The granules may be prepared via an extrusion process, for example by extruding a premix of the microemulsifiable concentrate and other ingredients under relatively high pressure (typically in excess of 0.69 MPa (100 psi)). ) and cutting the resulting extrudate into short lengths. The resultant granules can then be dried.

In this process, the individual components may be combined in any sequence and combined in a suitable mixer and granulated using known methods and equipment for the production of granules. For example, the finely divided dispersing filler material may be combined with water and added before, during or after the combination of the dry ingredients. Alternatively, the dispersant may be dissolved first in the water used for the combination. The microemulsifiable concentrate comprising the active chemical agent (s) may be combined with the other components used to form the granules prior to extrusion. After the granules are formed, they are then dried to remove excess moisture. Granules that are prepared by the active chemical by an extrusion process can subsequently be sprayed with the microemulsifiable concentrate comprising the chemical agent (s). ) active (s) for adhering agent (s) to the granules. The sprayed granules are then dried, for example, in a fluid bed dryer to the desired moisture content.

Granules may also be prepared by coating a core granule with an absorbent coating of filler particles. A microemulsifiable concentrate comprising chemically active materials may then be loaded onto the surface of the granules. The amount of water used may vary depending on the desired absorptive capacity of the inert granules, which may be controlled by varying the ratio of filler materials. Granulation conditions may also have an influence on a required amount of water. Typically the amount of water may range from about 5kg to about 150kg per 100kg of dry mix (dispersant filler materials) and more typically is about 20 to about 70kg water / 100kg of dry mix.

UK Patent 1,304,543 discloses a process in which absorbent granules are prepared, and solutions of active substances or liquid substances are absorbed into the granules. These compositions are granules which are calcined zeolites of several hundred microns in diameter.

Preformed granules may be stored, and then used to absorb a predetermined amount of pesticide-reactive material at an appropriate time and place. The microemulsifiable concentrates of the present invention may be sprayed onto the granules, for example, in order to distribute the substance on the surface of the absorbent granules as quickly as possible. The spray can be introduced through air atomization nozzles to ensure spreading of the liquid active substance of the granules. Uniform spray jets in some cases will be appropriate. The amount of pesticide active material that is absorbed on the granule will vary depending on the fine use! desired as well as the ability of granules to absorb the formulations.

When loading the preformed granules with the active chemicals, uniform granule loading can be achieved. Balance between unevenly charged granules is believed to occur over substantial periods of time. Where the absorbance of the granule must be substantially fully saturated then the liquid can simply be poured over the agitated granules and granules until they become fully saturated.

Preferably, the granules are partially saturated. For example, when the carrying capacity is about 40 percent, it is preferred to only charge at about 32 percent, that is, about 80 percent of its capacity. It is preferable to load the granules at about 60 to about 90 percent and more preferably about 70 to about 85 percent of their capacity. That said, since pesticide-active materials are effective at relatively low concentrations, and fertilizers are applied at relatively high concentrations, the weight ratio of pesticide-active materials to the rest of the granule components is often relatively low.

Many dry mass granular fertilizers, and other inert granules, may be impregnated or coated with the microemulsifiable concentrates of the present invention. Where application of the microemulsifiable concentrates of the present invention to dry mass granular fertilizers would follow in all directions for use and precautions in the respective product labels, with reference to target crops, rates per acre, soil texture, application methods (including application timing) and rotational harvesting, to ensure that the granules are compatible with anticipated use of the compositions.

Granule formulations may be prepared, for example, using any sealed drum, mat, tape, or other commonly used dry mass deferring mixer. Nozzles used for spraying microemulsifiable concentrates on the granules are ideally placed in an appropriate position, and properly aimed, to provide uniform spray coverage. Care should be taken to aim the spray directly on the granules, and to avoid spraying of the mixer walls.

Those skilled in the art can readily determine how much chemically active ingredient to add to the granules. For example, one can simply consider the application rate of the granules in their intended use (e.g., with a fertilizer), and the chemically active doingredient application rate, and determine an appropriate reason for adding such materials to the granules.

The granules may also be prepared by shaping the powdery ingredients, optionally including the microemulsifiable concentrate, and milling them to provide the desired particle size, then subsequently turning the powder into granules over a range of particles. techniques including agglomeration, spray drying or other media such as drum granulation.

The granules may be prepared by mixing and pelleting the individual components. The transformation into pellets can be accomplished using conventional pelletizing equipment such as pelletizing drum and drum granules. The resulting pellet granules are then generally dried to remove excess moisture. Granules which are prepared in the absence of the active chemical by an extrusion process may subsequently be sprayed with microemulsifiable concentrates comprising the active chemical agent (s) to adhere to the active chemical (s). ) stick to the granules.

The granules may be dried using any suitable medium (eg on trays) that does not result in friction or damage. They may be dried under elevated temperature and / or under vacuum. Static delight and strip dryers may be used, although fluid bed dryers and rotary drum dryers may be preferred because of their relative effectiveness.

The resultant granules may then be sieved, if desired, to remove oversized or oversized granular substrates. Improperly sized material can be recycled to the mixing stage or milled to the appropriate size and re-sieved. Optionally, the finished product may be sprayed with a lightweight mineral oil to prevent product sprinkling into bulky form.

Finished product specifications of apparent density and sizing will impact how granules can be applied. Granule size can be determined, for example, by the uniformity index / size guide number system used in the fertilizer industry. The size guide number describes the relative department size and is obtained by multiplying the average particle size in millimeters. The index is expressed as an integer between 1 and 100 with higher numbers indicating better uniformity and tighter range. Additionally, the sizing may be determined according to ASTM E 728091 volume 11.04 wherein the sizing is preferably 20% or more passing through a 14 mesh screen and is retained in a 40 mesh screen.

The ideally manufactured granular substrate is strong enough that the particle does not degrade during normal handling and transport operations. Degradation of granular substrates would result in an increase in thin material which in turn would increase bulk density. In addition, dust or dust material absorbs more chemical agent and thus would result in improper distribution of the active chemical in the application.

Preferably, the granular substrate will not degrade until it is subjected to water. Degradation would also be minimized when subjected to high humidity.

The granules may be applied with a dry spreader, such as a rotary or drop spreader, to a target area. The active chemical agents can then associate with water, if applied by the natural user, such as rain or dew, and readily spread to the surrounding environment.

The present invention will be better understood with reference to the following non-limiting examples.

Microemulsifiable concentrate formulations 1 and 2 were prepared by combining the solvents in a blender and leaving the blender. The surfactants were heated to reduce their viscosity and added to the mixer. The fused Iambda-Cyhalothrin technique was then added and the composition was mixed until homogeneous. The vehicle granules used were uniform, round granules consisting mainly of wood dust and dolomitic limestone with a mean diameter of 1.5 mm. The granules were loaded into a Munsen mixer. While mixing, the liquid microemulsifiable concentrations were sprayed onto the granules.

Microemulsifiable Concentrate 1 (MEC 1) <table> table see original document page 24 </column> </row> <table>

Microemulsifiable Coentrant 2 (MEC2)

A granular material comprising lambda-cyhalothrin, outside the scope of the present invention and described below as comparative granule 1, was prepared as described above, except that the composition contained no surfactant.

Comparative Granule 1 (Length 1)

<table> table see original document page 24 </column> </row> <table>

The above formulations were applied to carrier granules which were uniform, round granules consisting primarily of wood dust and dolomitic limestone with an average diameter of 1.5 mm. The formulations were applied which direct a granule containing 0.045 wt.% Lambda-cyhalothrin.

A known amount of the treated vehicle was added to a 100 ml cylinder and about 75 ml of water was added to the top of the vehicle and allowed to settle for 20 seconds with no agitation. The supernatant was removed with a long plastic pipette and filtered through of a 0.2 micron filter to remove any suspended particles. The filtered supernatant was analyzed for lambda-cyhalothrin. The lambda-cyhalothrin extraction results shown in Table 1 represent the concentration of lambda-cyhalothrin found in the supernatant in micrograms per milliliter.

Table 1: Lambda-cyhalothrin concentration in water (g / ml)

<table> table see original document page 25 </column> </row> <table>

As can be seen from the data in Table 1, the granular formulations of the present invention release lambda-cyhalothrin much more readily than a similar formulation that does not contain an emulsifier system. This allows the most protament active ingredient to associate with water migration, thereby increasing the coverage of pesticide-active material in the target area.

The following procedures were used to prepare active ingredient treated granules and to measure the release of active ingredient in water migrating through the granules.

Spray solutions were prepared as follows: Sopro-phor®BSU - triestyrylphenol ethoxylate with about 16 moles available Rhdia ethoxylation, Soprophor® 3D33 and Toximul® 8320 were heated in an oven at 50 ° C overnight. another for melting and fluidizing the surfactants were inverted several times to mix before use. The same was done for Propiconazole and Lambda cyhalothrin techniques but at 75 ° C. The solvents, THFA and / or propylene carbonate, were added to a clean stainless steel province. While settling with a magnetic stirrer, all remaining ingredients were added. The solutions were allowed to mix until all ingredients were completely dissolved.

Granules were prepared as follows: 200 grams of size 8/16 Agsorb LVM granules were placed in a reflector drum. Tamping was started and spray solutions were applied using a conventional trigger spray on the descending granule curtain. The amount of liquid applied was determined gravimetrically by weight of the spray bottle after each spray until the desired amount was applied. After application, the granules were allowed to roll for about 15 minutes. A new spray bottle was used for each solution to prevent contamination from previous solutions.

A 24 cm (# 5) Whatman paper filter was folded into a cone and placed in a clean plastic funnel that was large enough to accommodate the filter. The filter was pre-wetted with 3 ml of tap water to adhere the filter to the funnel as is common practice. 75 grams of granules were added to the filter. 110 ml of tap water was poured into the granules. A small glass jar was placed under the funnel to capture the water passage. Once 25 ml had crossed, the lid was removed and capped. The amount of active ingredient in the phasase was measured via analytical methods. For the sample prepared with Iambda cyhalothrin formulations, the tap water was acidified with 0.1% acetic acid to prevent Iambda cyhalothrin hydrolysis while awaiting chemical analysis. This water was used for both granules formulated by Iambda cyhalothrin for consistency. Details regarding spray solutions, treated granules and analytical results showing the active ingredient in the aqueous phase are given below. Formulations used to study increased release of active ingredient from granulesSpray solutions

<table> table see original document page 27 </column> </row> <table>

Treated Granules

<table> table see original document page 27 </column> </row> <table>

* Comparative examples: compositions outside the scope of the present invention.

Analytical results for active ingredient content (μς a.i./ml) in aqueous phase <table> table see original document page 28 </column> </row> <table>

(too low to accurately determine)

As can be seen from the above data, the granular formulations of the present invention release the active ingredients much more readily than a similar formulation that does not contain a emulsifier system. This allows the active ingredient to more readily associate with water migration, thereby increasing the coverage of pesticide-active material in the target area.

While only a few exemplary embodiments of this invention have been described in the above details, those skilled in the art will readily appreciate that many modifications are possible in exemplary embodiments without materially departing from the novel teachings and advantages of this invention. Correspondingly, all such modifications are intended to be included within the scope of this invention as defined in the following claims.

Claims (31)

Dry dispersible or spreadable granule characterized by pellet comprising: (i) a solid carrier, (ii) at least one substantially water-insoluble active chemical; and (iii) an emulsifier system capable of forming a microemulsion of at least one substantially water-insoluble active chemical (ii) upon dilution with water. Granule according to Claim 1, characterized in that the substantially water-insoluble active chemical comprises at least one pesticide. Granule according to Claim 2, characterized in that the substantially water-insoluble chemical comprises at least one pesticide selected from the group consisting of herbicides, fungicides, insecticides, miticides, acaricides, molluscicides, nematodes, bacteriacides. , plant growth regulators and insect growth regulators. Granule according to Claim 1, characterized in that the chemical has a water solubility in water deionized at 20 ° C of not more than 5000 mg / l. Granule according to Claim 1, characterized in that the emulsifier system comprises at least one nonionic surfactant. Granule according to Claim 5, characterized in that the emulsifier system comprises a castor oil damping product and a P10 Cl2-4 alkylene oxide. Granule according to Claim 1, characterized in that the emulsifier system comprises at least one nonionic surfactant having an HLB> 9 and at least one hydrophobic anionic surfactant. Granule according to Claim 1, characterized in that the solid carrier is an inert material. Granule according to Claim 6, characterized in that the solid carrier is a dispersible granule. Granule according to Claim 1, characterized in that the solid carrier is a fertilizer material. A method of producing dried dispersible or dispersible granules containing at least one active chemical agent, characterized in that the application to or incorporation into a solid carrier (i) at least one substantially water-insoluble active chemical agent; and (ii) an emulsifier system capable of forming a microemulsion of at least one substantially water-insoluble active chemical upon dilution with water. The method according to claim 11, characterized in that the substantially water-insoluble chemical comprises at least one pesticide. The method according to claim 12, wherein the substantially water-insoluble chemical comprises at least one pesticide selected from the group consisting of herbicides, fungicides, insecticides, miticides, acaricides, molluscicides, nematides, bacteriacides. , plant growth regulators and insect growth regulators. A method according to claim 11, characterized in that the chemical has a water solubility in water deionized at 20 ° C of no more than 5000 mg / l. A method according to claim 11, characterized in that the emulsifier system comprises at least one nonionic surfactant. A method according to claim 15, characterized in that the emulsifier system comprises a castor oil damping product and a polyC 2-4 alkylene oxide. A method according to claim 11, characterized in that the emulsifier system comprises at least one nonionic surfactant having an HLB> 9 and at least one anionic hydrophobic surfactant. A method according to claim 11, characterized in that the solid carrier is an inert material. A method according to claim 18, characterized in that the solid carrier is a dispersible granule. The method according to claim 11, characterized in that the solid carrier is a fertilizer material. A method of producing dried dispersible or dispersible granules according to claim 11 which comprises: i) preparing at least one microemulsifiable concentrate comprising at least one substantially water-insoluble active chemical and a system emulsifier; and (ii) applying the microemulsifiable concentrate to or incorporating the microemulsifiable concentrate into a solid carrier. Method of providing an active chemical agent to a site to be treated, characterized in that it comprises: i) application on the site of a dry dispersible or spreadable granular composition comprising a) a carrier, b) at least one agent Substantially water-insoluble active chemical; and c) an emulsifier system capable of forming a microemulsion of the substantially water-insoluble active chemical agent (b) in water dilution; and (ii) allowing said dry granular composition to be contacted with water. The method of claim 22, wherein the substantially water-insoluble chemical comprises at least one pesticide. A method according to claim 22, wherein the substantially water-insoluble chemical comprises at least one pesticide selected from the group consisting of herbicides, fungicides, insecticides, miticides, acaricides, molluscicides, nematides, bacteriacides. , plant growth regulators and insect growth regulators The method according to claim 22, characterized in that the chemical has a water solubility in water deionized at 20 ° C of no more than 5000 mg / l. A method according to claim 22, characterized in that the emulsifier system comprises at least one nonionic surfactant. Granule according to Claim 26, characterized in that the emulsifier system comprises a castor oil condensation product and a POÜC2-4 alkylene oxide. A method according to claim 22, characterized in that the emulsifier system comprises at least one nonionic surfactant having an HLB> 9 and at least one anionic hydrophobic surfactant. A method according to claim 22, characterized in that the solid carrier is an inert material. A method according to claim 29, characterized in that the solid carrier is a dispersible granule. The method of claim 22, wherein the solid carrier is a fertilizer material.